WO2009043585A1 - Assemblage de matières nanostructurelles à nanofibres encapsulées dans des nanotubes - Google Patents

Assemblage de matières nanostructurelles à nanofibres encapsulées dans des nanotubes Download PDF

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WO2009043585A1
WO2009043585A1 PCT/EP2008/008383 EP2008008383W WO2009043585A1 WO 2009043585 A1 WO2009043585 A1 WO 2009043585A1 EP 2008008383 W EP2008008383 W EP 2008008383W WO 2009043585 A1 WO2009043585 A1 WO 2009043585A1
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carbon
carbon nanofibers
cnts
cnt
nanofibers
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Dangsheng Su
Jian Zhang
Robert SCHLÖGL
Joachim Maier
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MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Priority to US12/681,385 priority Critical patent/US20100285354A1/en
Publication of WO2009043585A1 publication Critical patent/WO2009043585A1/fr

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    • C01B32/158—Carbon nanotubes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82—NANOTECHNOLOGY
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    • H01G11/22—Electrodes
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    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/90—Selection of catalytic material
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    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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    • C01B2202/00—Structure or properties of carbon nanotubes
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    • C01B2202/28—Solid content in solvents
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    • C01B2202/00—Structure or properties of carbon nanotubes
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    • C01B2202/36—Diameter
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y10T428/292—In coating or impregnation

Definitions

  • the present invention relates to a method for producing carbon nanotube encapsulated carbon nanofibers (CNFs @ CNTs) nanostructure materials with one-dimensional structure, the products obtained thereby and the useo thereof.
  • CNFs @ CNTs carbon nanotube encapsulated carbon nanofibers
  • Carbon nanotubes are nanosized cylindrical structures made of carbon. CNTs are classified in single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT).
  • SWNT single-walled carbon nanotube
  • MWNT multi-walled carbon nanotubes
  • a single-walled carbon nanotube iss a one atom thick sheet of graphite rolled up into a seamless cylinder with diameters in the order of several nanometers.
  • multi-walled carbon nanotubes consist of multiple layers of graphite that are arranged in concentric cylinders. CNTs having various dimensions are commercially available in large amounts and at reasonable prices. 0
  • CNFs carbon nanofibers
  • Carbon nanofibers may be prepared via catalytic decomposition ofo hydrocarbons.
  • Pham-Huu et al. (Phys. Chem. Chem. Phys. 2002, 4, 514- 521 ) report on the synthesis of uniform carbon nanofibers by catalytic decomposition of ethane over a nickel catalyst supported on carbon nanotubes via a catalytic chemical vapour deposition process. Since the nickel catalyst is exclusively located on the outer wall of the carbon nanotubes carbon nanofibers are formed around the CNT catalyst support. The obtained nanotube-supported nanofibers may be employed as catalyst support due to their high external surface area.
  • Liu et al. (Carbon 43 (2005) 1557-1583) describe the preparation of carbon nanocoils using activated carbon nanotubes as catalyst support.
  • Nickel particles having a diameter of about 800 nm are deposited on activated carbon nanotubes.
  • Catalytical chemical vapour deposition using ethylene has been performed to obtain carbon microcoils attached to the activated carbon nanotubes. Due to the dimension of the nickel particles compared to the cavity of the CNT catalyst support formation of carbon coils within the cavity of the carbon nanotube can be excluded. The materials obtained are suggested to be used as support in catalytic reactions.
  • Carbon nanofilaments especially carbon nanotubes, have been suggested as a potential material to incorporate various compounds such as gases, ions, molecules, catalysts, etc. since the nanochannel inside of CNTs offers enough space to accommodate them.
  • the unique one-dimensional tubular structure of CNTs, their high electrical conductivity and large surface area are promising features for highly efficient storage properties.
  • the total pore volume is composed of firstly the hollow nanochannel of the carbon nanotubes, secondly the interstitual pores that are formed by aggregation of the carbon nanotubes into bundles and thirdly, in case of multi-walled carbon nanotubes, the interlayer space between the coaxial cylindrical carbon layers.
  • EP-A-1 591 418 describes a carbon tube-in-tube (CTIT) nanostructure material, wherein a tube with a higher average diameter compared to the pristine CNT and/or a tube with a lower average diameter compared to the pristine CNT is formed coaxially to the pristine CNT via a self-assembly process.
  • CTITs are suggested to be used as a catalyst support, electrode material for gas storage or as templates for the assembly of heterostructures.
  • Luzzi et al. disclose the manufacture of carbon C 6 o-cage structures within single-walled carbon nanotubes.
  • the cage structures internal to the SWNTs are found to be C 6 o fullerenes resembling nanoscopic peapods.
  • Fullerenes have a regular spherical carbon structure. The fullerenes are separated from the tube by 0.3 nm at the closest point.
  • the peapods are found to coalesce into capsules and interior tubes under prolonged exposure to an electron beam, whereby the inner tubes are coaxially aligned to the inner wall of the carbon nanotube.
  • Lithium-ion rechargeable batteries are one of the greatest successes of modern electrochemistry. Their applications are not only for consumer electronics but, most importantly, for green energy storage and potential use in hybrid electric vehicles (M. Endo et al. Carbon 38, 183 (2000): I. Maier, Nature Mater. 4, 805 (2005): A. S. Arico et al., Nature Mater. 4, 366 (2005)).
  • Carbon as a richly available and low-cost resource is a promising negative electrode material for lithium secondary batteries.
  • the limits in performance of the current synthetic/natural graphite electrode materials have been reached.
  • next-generation of Li-ion-battery electrodes is expected to have a higher reversible capacity as well as superior cycling stability (cyclability). Rapid development of carbon nanofilaments provides new opportunities also in Li- ion-battery elecrodes technology (see above and A. Oberlin et al. J. Cryst. Growth 32, 335 (1976); S. lijima, Nature 354, 56 (1991); Y. Zhang et al. Science 285, 1719 (1999)).
  • This problem is solved by the present invention by providing a method for producing carbon nanotube encapsulated carbon nanofibers (CNFs @ CNTs).
  • the strategy for producing CNFs @CNTs is based on a three-step procedure (Fig. 1).
  • a carbon nanotube starting material is provided.
  • This material may be subjected to a functionalization procedure, e.g. by an HNO 3 -based oxidation at defective sites, a process previously used to purify, cut or open nanotubes.
  • the oxidation concomitantly functionalizes the walls of carbon nanotubes with chemically reactive groups, e.g. carboxyl and/or hydroxyl groups.
  • the functionalization renders the carbon nanotubes starting material hydrophilically.
  • a catalytically active substance such as metallic cobalt, is deposited inside the channels of the CNT starting material.
  • the catalyst-modified carbon nanotubes are contacted with carbon- containing compounds, such as unsaturated hydrocarbons, e.g. ethyne or ethene, that are converted to carbon nanofibers at the active sites of the catalysts.
  • carbon- containing compounds such as unsaturated hydrocarbons, e.g. ethyne or ethene
  • the present invention relates to a method for producing carbon nanotube encapsulated carbon nanofibers nanostructure material comprising the steps a) providing a carbon nanotube (CNT) starting material, b) optionally subjecting the CNT material to a functionalization procedure, wherein a CNT starting material having chemically reactive groups is ob.tained, c) depositing at least one catalytically active substance in the interior of the CNT starting material having chemically reactive groups.
  • the starting materials for the method of the invention are carbon nanotubes (CNTs).
  • Carbon nanotubes may be present in the process as single-walled carbon nanotubes (SWNT) and/or multi-walled carbon nanotubes (MWNT).
  • SWNT single-walled carbon nanotubes
  • MWNT multi-walled carbon nanotubes
  • the CNT starting material of the present invention comprises multi-walled carbon nanotubes.
  • the nanotubes have an average inner diameter of about 10 to 150 nm and preferably from 20 to 80 nm.
  • the outer diameter of the carbon nanotubes starting material is of about 15 to 300 nm, preferably of about 50 to 200 nm.
  • the average length of the CNT starting material is of about 0.2 to 50 ⁇ m, preferably of about 2-50 ⁇ m, more preferably of about 20 ⁇ m.
  • the commercial CNTs used have preferably a substantially opening characteristic, i.e. at least 25% of CNTs are open, what allows both the catalytically active substance and the carbon containing compound to be easily diffused into the tubular channel.
  • the CNT starting material may be an as-synthesized sample, which has not been subjected to any purification procedure.
  • the content of impurities may be from about 0.2% to about 7% based on the weight of the total CNT starting material.
  • the first step according to the method of the present invention is a functionalization procedure that comprises an oxidation, wherein CNT walls having hydroxyl and/or carboxyl groups are formed.
  • the oxidation comprises heating the CNT starting material with HNO 3 or HNO 3 /H 2 SO 4 .
  • the oxidation comprises treatment with concentrated HNO 3 at about 90-130 0 C for about 30 min to about 48 hours.
  • the functionalization procedure comprises treatment with a solution of HNO 3 and H 2 SO 4 , wherein the volume ratio of HNO 3 to H 2 SO 4 is preferably 0.2-5:1.
  • the as-treated nanotubes are subsequently dried at 80-100 0 C for about 1-15 hours.
  • the hydroxyl and/or carboxyl groups formed during the functionalization procedure render the walls of the CNTs hydrophilically and thus, establish improved conditions for the incipient wetness impregnation procedure (see below).
  • the second step of the invention further comprises depositing catalytically active substances inside, preferably selectively inside, the channels of the CNT material obtained in the first step.
  • the catalytically active substance comprises metals, alloys or metal compounds, preferably transition metals, alkaline metals or alkaline earth metals and/or alloys thereof and/or compounds thereof, more preferably iron, nickel, cobalt and/or alloys thereof and/or compounds thereof.
  • the metals, alloys or compounds may be present in elemental form, as oxides or salts.
  • the catalytically active substances or precursors thereof such as soluble metal salts or gaseous metal complexes, are preferably contacted with the hydrophilic carbon nanotubes in a suitable fluidic, e.g. liquid and/or gaseous, medium (water, ethanol, supercritical CO 2 , etc.) under suitable deposition conditions.
  • a suitable fluidic e.g. liquid and/or gaseous, medium (water, ethanol, supercritical CO 2 , etc.
  • the precursors are preferably salts selected from the group consisting of halides, nitrates or sulfates of the catalytically active metals mentioned above.
  • the volume of a fluidic medium containing the catalytically active substance or the precursor thereof corresponds to the volume of the inner channel of the carbon nanotubes.
  • the obtained material may be dried at about 80-120 0 C, preferably at about 100 0 C, for about 1-18 hours, preferably for about 10 h, and calcined under suitable conditions at 200-800°C, preferably at about 350°C, for about 1-6 hours, preferably for about 2 hours, in an inert gas environment, such as He, Ar, N 2 , or in air.
  • an inert gas environment such as He, Ar, N 2 , or in air.
  • a precursor of the catalytically active substance any suitable reaction may be conducted in order to obtain the catalytically active species.
  • the precursor may be reduced, oxidized, heated, or activated with suitable reagents.
  • an effective amount of the catalytically active substance e.g. about 0.001- 7%, preferably about 0.1-5%, more preferably about 0.5% based on the total weight of the carbon nanotubes is deposited. It is obvious for one skilled in the art that the effective amount of catalytically active substance depends from the reaction conditions, the respective catalyst material as well from the carbon containing compound used in step d) (see below).
  • the catalytical active substance may be deposited in form of discrete catalyst agglomerates, preferably in form of catalyst nanoparticles having an average diameter of about 1-10 nm, preferably from about 2-7 nm.
  • the catalyst-modified CNTs from step c) can be pre-treated at elevated temperatures under reducing conditions. Surprisingly it has been found that such a pre-treatment improves the activity of the catalyst.
  • Suitable activation comprises treating the modified CNTs at temperatures of up to about 350 0 C, preferably of up to about 700 0 C in a reducing gas/inert gas atmosphere.
  • the reducing gas may be hydrogen or ammonia or carbon monoxide.
  • the volume ratio of reducing gas/inert gas (N 2 , He, Ar) is preferably of about 1 :1 to 1 :3.
  • step d) the CNTs obtained in step c) are contacted with at least one carbon-containing compound, which is capable of decomposing and forming carbon nanofibers in the presence of the catalyst in order to obtain carbon nanotube encapsulated carbon fibers.
  • the carbon nanotube encapsulated carbon fibers are prepared via a catalytic chemical vapour deposition process (CCVD).
  • CCVD catalytic chemical vapour deposition process
  • Catalytic chemical vapour deposition is well-known in the art and comprises the deposition of a solid phase component from a gas phase onto the surface of a substrate due to a catalytic reaction.
  • Carbon-containing compounds are preferably deposited from the gas phase.
  • the compounds are preferably gaseous carbon-containing compounds selected from the group consisting of saturated and/or unsaturated, optionally substituted, hydrocarbons, such as ethane, CH 3 CI, ethylene, and/or ethyne, but also CO may be used.
  • Deposition of CNFs preferably is adjacent to the catalyst nanoparticles.
  • the carbon-containing compound is contacted with the catalyst- modified carbon nanotubes at elevated temperatures of up to 700 0 C, preferably from about 200-500 0 C, more preferably from about 350-480 0 C.
  • the carbon-containing compound is introduced to the CNTs via a constant flow.
  • the carbon containing compound may be present in dilution with an inert and/or reducing gaseous atmosphere.
  • the inert gas may be e.g. a noble gas or nitrogen
  • the reducing gas may be e.g. hydrogen or suitable non- carbon containing reducing gases. It has been found, that the CCVD conducted under reducing atmosphere leads to better CNF yields.
  • the reducing gas/inert gas mixture may be the same used in the pre-treatment step (see above).
  • the volume ratio of carbon containing compound/gas mixture is preferably 1 :1.
  • the ratio of the carbon-containing compound to the catalyst material can vary from 0.2 to about 10 l/g depending from the type of catalyst and the carbon-containing compounds used.
  • the duration of the CCVD process is dependent from the compound, the catalyst, the flow rate etc. and is preferably in the range of 5 min to 2 hours, more preferably 5-20 min..
  • the reaction product is allowed to cool down to room temperature, preferably in an inert gas atmosphere, such as helium, argon or nitrogen.
  • an inert gas atmosphere such as helium, argon or nitrogen.
  • the carbon nanofiber formed in step has a crimped morphology.
  • a "crimped morphology” means that the CNF may be curved or curled, preferably the CNF is in the form of a random coil as known from peptides and polymers (see e.g. Flory, P.J. (1969) Statistical Mechanics of Chain Molecules, Wiley),.
  • the surface of the CNF may be smooth or rough.
  • the individual CNFs are randomly arranged to each other.
  • the carbon nanofibers according to the invention are hollow and may be open and/or closed.
  • the carbon nanofibers are open since the specific surface of the carbon nanotube encapsulated carbon nanofibers is increased even more in this case.
  • the carbon nanofibers have an average outer diameter of about 2-20 nm, preferably of about 5-15 nm, more preferably of about 8-12 nm and even more preferably of about 10 nm.
  • the average inner diameter of the carbon nanofibers is of about 0.5 to 15 nm, preferably of about 1 nm to 10 nm.
  • the carbon nanofibers according to the invention have a length of about 100-1000 nm, preferably of about 150-250 nm, more preferably of about 200 nm.
  • the aspect ratio of the CNFs 1 i.e. the ratio of length to the outer diameter is preferably more than about 2, preferably more than about 10 and even more preferably more than about 20.
  • the ratio of the inner diameter of the CNT material to the outer diameter of the carbon nanofibers lies in the range of from about 1 to 50, preferably from about 2 to 15.
  • the CNFs are selectively located within the channel of the carbon nanotubes, i.e. substantially none of the nanofibers are attached to the outer wall of the CNTs. Moreover, the nanofibers located at the tip of the nanotubes may be flush with the tip of the nanotube. Thus, substantially no CNFs protrude from the pristine CNTs. Said morphology assures an improved bulk density of the inventive CNFs @ CNTs due to the absence of any fluffy attachments outside the carbon nanotubes.
  • the CNFs do not show any preferred orientation with respect to the inner channel of the carbon nanotube, i.e. the linear CNT shape does not induce any directed growth of the CNFs.
  • the CNFs are randomly arranged within the interior of the CNT starting material.
  • the CNFs are not coaxially or co-parallel oriented with repect to the longitudinal axis of the pristine CNT.
  • Step e) of the method according to the invention comprises a thermal treatment.
  • the thermal treatment is preferably carried out by heating the carbon nanotube encapsulated carbon nanofibers obtained in step d) at temperatures of 800 0 C or higher, preferably of at least 1000 0 C to 2800°C preferably in an inert, e.g. N 2 , argon or noble gas, atmosphere.
  • the thermal treatment may lead to a structural condensation and/or improvement of the nanostructure.
  • the obtained products may optionally subjected to a purification step f), preferably in order to remove residual catalyst traces introduced in step c).
  • the CNFs @ CNTs are contacted with reagents capable of removing remaining catalyst traces from the obtained products.
  • suitable agents are nitric acid, sulfuric acid or a combination thereof, but are not limited thereto.
  • the carbon nanotube encapsulated carbon nanofibers are preferably characterised by a CNF/CNT weight ratio of about 10 to 60% by weight preferably of about 15 to 30%.
  • CNTs can be calculated from the increase in weight after step d), since it has been found by spectroscopical analysis that the weight increase during step d) of the inventive method is substantially assigned to the formation of carbon nanofibers.
  • At least 10, preferably 15 to 90% and more preferably 20 to 70% by volume of the volume of the inner channel of the CNT may be occupied by carbon nanofibers.
  • the specific surface area of the CNFs (S) CNTs is preferably higher than about 150 m 2 /g, preferably higher than about 250 m 2 /g and still more preferably higher than about 350 m 2 /g up to 1200 m 2 /g.
  • the CNFs (S ) CNTs products possess a higher porosity compared to that of pristine CNTs and other modified CNTs, such as CTITs.
  • the pore volume of the CNFs @ CNTs is higher than 0.5 cm 3 g "1 and more preferably of about from 0.6 to 5 2.0 cm 3 g- 1 .
  • a further aspect of the present invention is a carbon nanotube encapsulated carbon nanofibers nanostructure material obtainable by the method as described above.
  • a still further aspect of the present invention is a carbon nanotube encapsulated carbon nanofiber nanostructure material, wherein the carbon nanofibers inside the channel of the carbon nanotube have a crimped shape.
  • the carbon nanotube encapsulated carbon nanofibers are preferably characterised by a CNF/CNT weight ratio of about 10 to 60% by weight preferably of about 15 to 30%.
  • the CNFs @ CNTs products possess ao higher porosity compared to that of pristine CNTs and other modified CNTs, such as CTITs.
  • the pore volume of the CNFs @ CNTs is preferably higher than 0.5 cm 3 g "1 and more preferably of about from 0.6 to 2.0 cm 3 g "1 .
  • the pore volume of the CNFs @ CNTs is preferably increased by at least 200%, preferably by about 300% and more preferably by about 400% compared to5 that of pristine carbon nanotubes.
  • the specific surface area of the CNFs @ CNTs is higher than about 150 m 2 /g, preferably higher than about 250 m 2 /g and still more preferably higher than about 350 m 2 /g up to about 1200 m 2 /g.
  • the specific surface area of the CNFs @ CNTs is increased by at least 120%, preferably by at least 400% compared to that of pristine CNTs.
  • At least 10%, preferably 15-90% and more preferably 20 to 70% by volume of the volume of the inner channel of the CNT may be occupied by carbon nanofibers.
  • any above-mentioned properties of the CNFs @ CNTs obtained by the inventive method can also be transferred to the inventive carbon nanotube encapsulated carbon nanofibers nanostructure materials.
  • carbon nanotube encapsulated carbon nanofibers Due to the improved spatial utilization of the hollow channels compared to known carbon nanotube materials, it is expected carbon nanotube encapsulated carbon nanofibers to have reasonably potential applications in many important fields, e.g. as energy storage material, hydrogen storage material, electrode material, e.g. in Li-ion batteries, supercapacity material, as reinforcing or conductive additive in composite materials, as catalyst support and as filter material, e.g. waste water treatment for environmental protections.
  • CNFs @ CNTs are used as elecrode materials. Therefor, CNFs @ CNTs are formed to any suitable elecrode shape. In a preferred embodiment the CNFs @ CNTs nanostructure material is compressed using conventional press molds. Optionally, the CNFs @ CNTs nanostructure material is combined with any suitable binder material.
  • the binder material comprises any electrochemically resistant material, such as poly(vinyldifluoride) (PVDF).
  • the electrode is formed by applying a mixture of CNFs @ CNTs nanostructure material and binder material to a conductive substrate, such as a metal substrate.
  • the obtained CNFs @ CNTs electrode materials are used as a negative electrode in Li-ion batteries.
  • the electrolyte used in combination with the inventive electrode is a Li-ion containing salt, e.g. LiPF 6 or LiCIO 4 , that is soluble in any elecrochemically stable organic solvents, e.g. ethylene carbonate (EC) or propylenecarbonate (PC).
  • the counter electrode comprises any material suitable in Li-ion batteries, for example Lithium, Li x Mn 2 O 4 , Li x NiO 2 , Li x CoO 2 , wherein x is 0 to 3.
  • CNFs inside the CNT channels results in a greatly improved spatial utilization of the inner hollow channel of CNTs and thus improved specific density.
  • the CNFs @ CNTs with a higher spatial utilization have an outstanding reversible volumetric capacity and long-time stability.
  • the contribution to the porosity mainly comes from the secondary pores between CNFs and CNTs or from extremely stacking of CNFs inside CNTs because only the produced CNFs can not contribute to such a great extent (D. S. Su et al, Adv. Mater. 2007, to be published)
  • a further aspect of the present invention is a Lithium-ion battery comprising a negative electrode comprising CNFs @ CNTs nanostructure material, an positive electrode and a Li-containing liquid electrolyte.
  • CNFs @ CNTs electrode materials are used in supercapacitors exhibiting a capacity of 70 F/g.
  • the method according to the invention provides a template-free synthesis of carbon nanotube-encapsulated carbon nanofibers (i.e. CNFs @ CNTs) 1 by which cheap and low-quality commercial CNTs are modified into high- performance electrode materials.
  • CNFs @ CNTs carbon nanotube-encapsulated carbon nanofibers
  • SWNTs the CNTs used here have a lower surface area (82 m 2 g "1 ), bigger outer diameter (50-200 nm) and thicker walls (50-100 walls). Large-scale production makes their price as low as 50 USD per kilogram.
  • the CNFs @ CNTs exhibit an outstanding reversible capacity, cyclability and specific capacitance when used as an anode in lithium-based batteries and as an electrode material in supercapacitors, respectively.
  • Fig. 1 Sectional drawing of the synthesis route to CNFs @ CNTs.
  • FIG. 2 TEM images of 0.5% Co@CNTs after H 2 reduction.
  • A-B Bright- field HRTEM images;
  • C-E Dark-field STEM images.
  • FIG. 3 Morphologies of pristine CNTs and CNFs
  • S CNFs.
  • A SEM image of fresh CNTs.
  • B SEM image of CNFs @ CNTs.
  • C HRTEM image of CNFs @ CNTs.
  • D HRTEM image of typical synthesized CNFs. TEM images of the CNFs @ CNTs on the sample holder tilted at angles of: (E) -30°; (F) 0°; (G) 30°.
  • Fig. 6 Performance of carbon samples in Li electrochemical lithiation and delithiation tests.
  • A Galvanostatic discharge (Li insertion, voltage decreases)/charge (Li extraction, voltage increases) curves of CNFs @ CNTs that cycled at a rate of C/5 in 1 M LiPF 6 in EC/DMC solution.
  • B Cyclic voltammogram at a scan rate of 0.1 mV s "1 in the voltage range of 0.01 and 3 V in 1 M LiPF 6 in
  • FIG. 8 Performance of carbon samples in supercapacitor tests.
  • A Cyclic voltammograms of CNFs @ CNTs electrode at different scan rates in 1.0 M H 2 SO 4 solution.
  • B Galvanastatic discharge/charge curves cycled at current densities of 370 (solid line) and 740 (dot line) mA g "1 .
  • C Relationship between specific capacity and current density.
  • 0.5 g commercial carbon nanotubes PR-24-HHT, Applied Sciences, Inc., inner diameter : 20-80 nm
  • the obtained materials were dried at 100°C for 10 h, calcined at 350 0 C for 2 h in air, and then reduced at 400°C in a H 2 flow.
  • Metallic cobalt nanoparticles with average size of 6.6 nm were deposited on the channel wall of the CNTs (Fig. 2).
  • 3E- F proves a good confinement of CNFs, which mainly benefit from the success in preferential deposition of active metal nanoparticles on the inner walls.
  • Most nanotubes with open ends are filled with small CNFs.
  • Completely closed CNTs are hollow due to the absence of Co nanoparticles in the inner of the channel.
  • Micro-Raman spectra were recorded on a Jobin Yvon LabRam spectrometer using a 632.8 nm excitation laser line. SEM images were recorded using a Hitachi S4800 scanning electron microscope. TEM and STEM images were recorded on a Philips CM200 FEG and a CM200 LaB 6 transmission electron microscope operating at 200 kV.
  • Lithium intercalation / deintercalation tests were carried out in two-electrode SwagelokTM-type cells.
  • the working electrodes were prepared by mixing the carbon sample with poly(vinyldifluoride) (PVDF) by a weight ratio of 90:10 and pasting on pure Cu foil (99.6%, Goodfellow).
  • PVDF poly(vinyldifluoride)
  • Glass fiber D 1 Whatman ®
  • pure lithium foil Aldrich
  • the electrolyte consists of a solution of 1 M LiPF 6 in ethylene carbonate (EC) /dimethyl carbonate (DMC) (volume ratio 1 :1 ) obtained from Ube Industries Ltd or a solution of 1 M LiCIO 4 in propylene carbonate (PC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • Electrochemical performances were tested at different current densities in the voltage range of 0.01-3 V on an Arbin MSTAT battery test system. Cyclic voltammogram measurements were performed on VoltaLab ® 80 electrochemical workstation at a scan rate of 0.1 mV s ⁇ 1 .
  • Fig. 6A shows the discharge (Li insertion)/charge (Li extraction) curves of a CNFs @ CNTs electrode cycled in 1 M LiPF 6 ethylene carbonate (ECydimethyl carbonate (DMC) (volume ratio 1 :1) electrolyte at a rate of C/5 (one lithium per six formula units (LiC 6 ) in 5 hours).
  • DMC LiPF 6 ethylene carbonate
  • C/5 one lithium per six formula units
  • the sloped regions in the discharge/charge curves can be ascribed to the Li insertion/deinsertion into disordered structure of CNFs @ CNTs.
  • SEI solid electrolyte interphase
  • PC propylene carbonate
  • the PC solvent and the solvated Li + ions tend to co-intercalate into graphite accompanied by severe exfoliation of graphite layers and thus destruction of the graphite structure.
  • CNFs @ CNTs In the terms of stability of the high lithium storage capacity CNFs @ CNTs is superior to pristine CNTs. During 120 cycles, the reversible capacity of CNFs @ CNTs stayed at around 410 mA h g '1 while that of CNTs gradually decreased to 258 mA h g- 1 (Fig. 6D).
  • the volumetric ratio of C rev ,cNFs @ CNTS to C rev ,cN ⁇ s reaches a value as high as 2.02, in which the 25% of increase in bulk density was taken into account.
  • CNFs @ CNTs also possess a high rate capability.
  • the discharge/charge rate was enhanced from C/5 to 1 C, the reversible capacity still remained higher than 300 mA h g '1 over 50 cycles (Fig. 7).
  • the superior stability of CNFs @ CNTs to pristine CNTs might mainly arise from the steric hindrance effect of compact structure to suppress the diffusion of big electrolyte molecules over the defected walls.
  • the outstanding cycling performance with high storage capacity makes CNFs @ CNTs much more attractive than other carbon materials (e.g. MvVNTs, hard carbon or CNFs) reported in literature.
  • Supercapacitive performance was evaluated with a three-electrode configuration, in which a platinum foil, saturated calomel electrode (SCE) and sample electrode were used as counter, reference and working electrodes, respectively.
  • SCE saturated calomel electrode
  • the electrolyte (1.0 M H 2 SO 4 aqueous solution) was purged with Argon gas for 10 min prior to electrochemical measurements. Cyclic voltammogram and galvanostatic charge / discharge tests were carried out on a Solartron SI 1287 electrochemical interface.
  • CNFs @ CNTs also show a satisfactory supercapacitive performance.
  • the typical cyclovoltagramms recorded at different scan rates in 1.0 M H 2 SO 4 solution are presented in Figure 8A.
  • galvanostatic discharge/charge measurements were carried out at different current densities, whose results are shown in Figs. 8B and 8C.
  • the specific capacitance is ca. 70 F g ⁇ 1 at a current density of 148 mA g ⁇ 1 .
  • At higher current densities of 370 and 740 mA g ⁇ ⁇ capacitance values of ca. 48 and 40 F g '1 are obtained.
  • the method according to the invention provides a template-free synthesis of carbon nanotube-encapsulated carbon nanofibers (i.e. CNFs @ CNTs), by which cheap and low-quality commercial CNTs are modified into high- performance electrode materials.
  • CNFs @ CNTs carbon nanotube-encapsulated carbon nanofibers
  • SWNTs the CNTs used here have a lower surface area (82 m 2 g "1 ), bigger outer diameter (50-200 nm) and thicker walls (50-100 walls). Large-scale production makes their price as low as 50 USD per kilogram.
  • the CNFs @ CNTs exhibit a reversible capacity of 410 mA h g "1 over 120 charge/discharge cycles and a specific capacitance as high as 70 F g '1 when used as an anode in lithium-based batteries and as an electrode material in supercapacitors, respectively.
  • the method of the present invention provides a simple route to modify cheap commercial CNTs into highly efficient carbon for electrochemical energy storage.
  • the feedstock is cheap and each operation is well-established and easy to be industrialized.
  • CNFs @ CNTs with a higher spatial utilization displayed a reversible volumetric capacity two times of pristine CNTs and an outstanding long-time stability.
  • CNFs @ CNTs are also proved to be a good electrode material in supercapacitors. Due to their unique structural properties CNFs @ CNTs represent a new class of carbon hybrid materials with significant potential for applications in the fields of gas adsorption, environmental protection, waste water treatment, fuel cells, catalysis, hydrogen storage, etc.

Abstract

L'invention concerne des nanofibres de carbone encapsulées dans des nanotubes (CNF dans CNT), qui présentent une structure unidimensionnelle et sont produites par l'assemblage sélectif de nanofibres de carbone à l'intérieur du passage de nanotubes de carbone, par l'imprégnation d'un catalyseur dans les nanotubes de carbone et le dépôt chimique ultérieur en phase vapeur d'un hydrocarbure. Cette nouvelle structure s'utilise comme matière de stockage d'énergie.
PCT/EP2008/008383 2007-10-04 2008-10-02 Assemblage de matières nanostructurelles à nanofibres encapsulées dans des nanotubes WO2009043585A1 (fr)

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